JP2008147154A - Photoelectrochemical cell - Google Patents
Photoelectrochemical cell Download PDFInfo
- Publication number
- JP2008147154A JP2008147154A JP2007111460A JP2007111460A JP2008147154A JP 2008147154 A JP2008147154 A JP 2008147154A JP 2007111460 A JP2007111460 A JP 2007111460A JP 2007111460 A JP2007111460 A JP 2007111460A JP 2008147154 A JP2008147154 A JP 2008147154A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectrochemical cell
- glass frit
- semiconductor fine
- zinc
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 claims abstract description 59
- 239000011521 glass Substances 0.000 claims abstract description 39
- 238000007789 sealing Methods 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 51
- 230000002165 photosensitisation Effects 0.000 claims description 34
- 239000003504 photosensitizing agent Substances 0.000 claims description 34
- 239000000565 sealant Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 229910052796 boron Inorganic materials 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052714 tellurium Inorganic materials 0.000 claims 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims 1
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 50
- 239000010410 layer Substances 0.000 description 49
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 229910001887 tin oxide Inorganic materials 0.000 description 11
- -1 selenium Cadmium iodide Chemical compound 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
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- 238000010304 firing Methods 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
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- 239000000463 material Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
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- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 150000002496 iodine Chemical class 0.000 description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 150000002540 isothiocyanates Chemical class 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 238000002834 transmittance Methods 0.000 description 3
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- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 2
- IVCMUVGRRDWTDK-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1 IVCMUVGRRDWTDK-UHFFFAOYSA-M 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
Description
本発明は、太陽電池などの光電気化学電池に関する。 The present invention relates to a photoelectrochemical cell such as a solar cell.
近年、地球温暖化防止のために大気中に放出されるＣＯ２の削減が求められている。ＣＯ２の削減の有力な手段として、例えば、家屋の屋根などに設置し得るｐｎ接合型のシリコン系太陽電池などの光電気化学電池を用いるソーラーシステムの利用促進が提唱されている。しかしながら、上記シリコン系光電気化学電池に用いられる単結晶、多結晶及びアモルファスシリコンは、その製造過程において高温、高真空条件が必要なために高コストになるという問題があった。
一方、非特許文献１には、光増感色素を表面に吸着させた酸化チタンの薄膜を導電性基板に積層させた光電変換素子、電荷移動層及び対極を含む光電気化学電池が提案されている。該光電気化学電池は、従来のシリコン系太陽電池と比較すると、使用する材料の多くは安価で、製造過程においても高温高真空条件が必要でないことから、より安価になることが期待されている。
ところで、非特許文献１に提案されている電荷移動層は、電解質としてヨウ素・ヨウ化物等を用い、溶媒として用いるアセトニトリル等の揮発性溶媒を用いており、長期に使用する必要がある場合は、電荷移動層が揮発しないように封止剤が用いられる。
例えば、特許文献１に、鉛を含むガラスフリットを封止剤として用いた光電気化学電池が提案されている。
In recent years, in order to prevent global warming, reduction of CO 2 released into the atmosphere has been demanded. As an effective means for reducing CO 2 , for example, promotion of utilization of a solar system using a photoelectrochemical cell such as a pn junction type silicon solar cell that can be installed on a roof of a house has been proposed. However, the single crystal, polycrystal and amorphous silicon used in the silicon photoelectrochemical cell have a problem of high cost because high temperature and high vacuum conditions are required in the production process.
On the other hand, Non-Patent Document 1 proposes a photoelectrochemical cell including a photoelectric conversion element in which a thin film of titanium oxide having a photosensitizing dye adsorbed on its surface is laminated on a conductive substrate, a charge transfer layer, and a counter electrode. Yes. Compared to conventional silicon-based solar cells, the photoelectrochemical cell is expected to be cheaper because many of the materials used are inexpensive and high-temperature high-vacuum conditions are not required in the manufacturing process. .
By the way, the charge transfer layer proposed in Non-Patent Document 1 uses iodine / iodide or the like as an electrolyte, and uses a volatile solvent such as acetonitrile as a solvent. A sealant is used so that the charge transfer layer does not volatilize.
For example, Patent Document 1 proposes a photoelectrochemical cell using glass frit containing lead as a sealant.
本発明者らが、電荷移動層に含まれる電解質としてヨウ素・ヨウ化物を用い、溶媒としてアセトニトリルを用い、封止剤として鉛を含むガラスフリットを用いてなる光電気化学電池について検討したところ、該光電気化学電池を８５℃付近で保存すると、ヨウ素が一部消失してしまい、耐久性が十分ではないことが明らかになった。
本発明の目的は、高温で保存しても、電荷移動層に含まれる電解質や溶媒等の電荷移動層が失われず、耐久性に優れた光電気化学電池を提供することである。
The present inventors examined a photoelectrochemical cell using iodine / iodide as an electrolyte contained in a charge transfer layer, acetonitrile as a solvent, and glass frit containing lead as a sealing agent. It was revealed that when the photoelectrochemical cell was stored at around 85 ° C., some iodine disappeared and the durability was not sufficient.
An object of the present invention is to provide a photoelectrochemical cell excellent in durability without losing a charge transfer layer such as an electrolyte or a solvent contained in the charge transfer layer even when stored at a high temperature.
本発明者らは、上記課題を解決するため鋭意検討した結果、本発明に至った。すなわち、本発明は、導電性基板、光増感色素を吸着させた半導体微粒子、電荷移動層及び対極を含む積層体を、封止剤で封止してなる光電気化学電池において、バナジウム、ビスマス又は亜鉛を少なくとも一種を含むガラスフリットを用いることを特徴とする光電気化学電池である。 As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention relates to a photoelectrochemical cell in which a laminate including a conductive substrate, semiconductor fine particles adsorbed with a photosensitizing dye, a charge transfer layer, and a counter electrode is sealed with a sealant. Alternatively, a photoelectrochemical cell using a glass frit containing at least one kind of zinc.
本発明の光電気化学電池は、アセトニトリル等の揮発性溶媒やヨウ素などの電解質の揮発を防止できるため、耐久性に優れる。 The photoelectrochemical cell of the present invention is excellent in durability because it can prevent volatilization of a volatile solvent such as acetonitrile and an electrolyte such as iodine.
以下、本発明を詳細に説明する。
本発明の光電気化学電池は、導電性基板、光増感色素を吸着させた半導体微粒子、電荷移動層及び対極を含む積層体を、封止剤で封止してなる光電気化学電池である。
湿式光電気化学電池は、光増感色素を吸着させた半導体微粒子の層（以下、色素吸着半導体粒子層という場合がある）に接する導電性基板と対極との間に電解液が充填されている。
また、乾式光電気化学電池は、導電性基板と対極との間が、固体のホール輸送材料を介して積層されており、光増感色素を吸着させた半導体微粒子は固体のホール輸送材料中に含有されている。
Hereinafter, the present invention will be described in detail.
The photoelectrochemical cell of the present invention is a photoelectrochemical cell formed by sealing a laminate including a conductive substrate, semiconductor fine particles adsorbing a photosensitizing dye, a charge transfer layer, and a counter electrode with a sealant. .
In a wet photoelectrochemical cell, an electrolytic solution is filled between a conductive substrate in contact with a layer of semiconductor fine particles adsorbed with a photosensitizing dye (hereinafter sometimes referred to as a dye-adsorbing semiconductor particle layer) and a counter electrode. .
In the dry photoelectrochemical cell, the conductive substrate and the counter electrode are stacked via a solid hole transport material, and the semiconductor fine particles adsorbing the photosensitizing dye are contained in the solid hole transport material. Contained.
本発明の湿式光電気化学電池を例にして以下に説明する。具体例を図１に示した。導電性基板（８）と、該導電性基板（８）に対向する対極（９）と、これらの間に、光増感色素（４）が吸着された半導体微粒子層（３）が存在する。湿式光電気化学電池の場合は、（色素が吸着された）半導体粒子層（３）は電解液（５）で充填された状態で、封止材（１０）で封止されている。
導電性基板（８）は、上から順に基板（１）と導電層（２）で構成されている。対極（９）は、下から順に基板（７）と導電層（６）で構成されている。
The wet photoelectrochemical cell of the present invention will be described below as an example. A specific example is shown in FIG. A conductive substrate (8), a counter electrode (9) facing the conductive substrate (8), and a semiconductor fine particle layer (3) on which the photosensitizing dye (4) is adsorbed exist between these. In the case of a wet photoelectrochemical cell, the semiconductor particle layer (3) (with the dye adsorbed) is sealed with a sealing material (10) in a state filled with the electrolytic solution (5).
The conductive substrate (8) is composed of a substrate (1) and a conductive layer (2) in order from the top. The counter electrode (9) is composed of a substrate (7) and a conductive layer (6) in order from the bottom.
本発明の光電気化学電池に用いられる導電性基板（８）及び対極（９）における導電層（導電性基板としては（２）、対極としては（６））としては電気抵抗が低いほど好ましい。また、導電性基板の導電層（２）としては、高波長領域、具体的には３５０ｎｍより長波長側の領域で、高い透過率、具体的には８０％以上の透過率であることが好ましい。
導電層に用いられる導電性物質としては、例えば、鉄、ニッケル、クロム、チタン、アルミニウム、白金、金、銀、コバルト、パラジウム、銅、タンタル、ルテニウム、タングステン、亜鉛、錫等の金属；該金属のアロイ；インジウム−スズ複合酸化物（ＩＴＯ）、酸化スズにフッ素をドープしたもの等の導電性金属酸化物、炭素等が挙げられる。導電層は、これらの導電性物質を２種以上積層したものでも良い。
具体的な導電層としては、例えば、導電性物質そのもの、又は、不導体の基板表面に導電性物質の薄膜を蒸着、スパッタリング、接着等により形成したものなどが挙げられる。
導電性基板（８）は、入射した光を閉じ込め、有効に利用するために、導電性物質の表面にテクスチャー構造を有するものが好ましい。
対極（９）は、上記導電性物質からなるシートや箔が（７）の基板の役割を同時に果たしても良い。
The lower the electrical resistance of the conductive layer (the conductive substrate (2) and the counter electrode (6)) in the conductive substrate (8) and the counter electrode (9) used in the photoelectrochemical cell of the present invention is preferred. In addition, the conductive layer (2) of the conductive substrate preferably has a high transmittance in a high wavelength region, specifically a region longer than 350 nm, specifically a transmittance of 80% or more. .
Examples of the conductive substance used for the conductive layer include metals such as iron, nickel, chromium, titanium, aluminum, platinum, gold, silver, cobalt, palladium, copper, tantalum, ruthenium, tungsten, zinc, and tin; Alloy, conductive metal oxide such as indium-tin composite oxide (ITO), tin oxide doped with fluorine, carbon, and the like. The conductive layer may be a laminate of two or more of these conductive materials.
Specific examples of the conductive layer include a conductive substance itself or a nonconductive substrate surface formed by vapor deposition, sputtering, adhesion, or the like on a nonconductive substrate surface.
The conductive substrate (8) preferably has a texture structure on the surface of the conductive material in order to confine incident light and effectively use it.
In the counter electrode (9), the sheet or foil made of the conductive material may simultaneously serve as the substrate of (7).
導電性基板（８）及び対極（９）における不導体の基板（導電性基板としては（１）、対極としては（７））としては、ガラスなどが挙げられる。 Examples of the non-conductive substrate ((1) as the conductive substrate and (7) as the counter electrode) in the conductive substrate (8) and the counter electrode (9) include glass.
導電性基板（８）及び対極（９）としては、ガラス等に導電性の金属酸化物を塗布したものが好ましい。中でも、フッ素をドーピングした二酸化スズからなる導電層を積層した導電性ガラスが、電気抵抗が低く、光の透過性に優れ、入手もしやすいことから特に好ましい。 As an electroconductive board | substrate (8) and a counter electrode (9), what apply | coated electroconductive metal oxide to glass etc. is preferable. Among these, conductive glass in which a conductive layer made of tin dioxide doped with fluorine is laminated is particularly preferable because it has low electrical resistance, excellent light transmittance, and is easily available.
本発明に用いられる半導体微粒子とは、一次粒径が、１〜５０００ｎｍ程度、好ましくは５〜５００ｎｍ程度の半導体特性を有する微粒子である。反射による光電変換効率の向上を目的として、一次粒径の異なる半導体微粒子を混入させてもよい。また、チューブや中空形状の微粒子を用いてもよい。 The semiconductor fine particles used in the present invention are fine particles having a semiconductor characteristic with a primary particle size of about 1 to 5000 nm, preferably about 5 to 500 nm. For the purpose of improving photoelectric conversion efficiency by reflection, semiconductor fine particles having different primary particle diameters may be mixed. Tubes and hollow fine particles may be used.
半導体微粒子（２）の材質としては、例えば、酸化チタン、酸化スズ、酸化亜鉛、酸化鉄、酸化タングステン、酸化ジルコニウム、酸化ハフニウム、酸化ストロンチウム、酸化インジウム、酸化セリウム、酸化イットリウム、酸化ランタン、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化ガリウム、酸化ニッケル、チタン酸ストロンチウム、チタン酸バリウム、ニオブ酸カリウム、タンタル酸ナトリウム等の金属酸化物；ヨウ化銀、臭化銀、ヨウ化銅、臭化銅等の金属ハロゲン化物；硫化亜鉛、硫化チタン、硫化インジウム、硫化ビスマス、硫化カドミウム、硫化ジルコニウム、硫化タンタル、硫化モリブデン、硫化銀、硫化銅、硫化スズ、硫化タングステン、硫化アンチモン等の金属硫化物；セレン化カドミウム、セレン化ジルコニウム、セレン化亜鉛、セレン化チタン、セレン化インジウム、セレン化タングステン、セレン化モリブデン、セレン化ビスマス、セレン化鉛等の金属セレン化物；テルル化カドミウム、テルル化タングステン、テルル化モリブデン、テルル化亜鉛、テルル化ビスマス等の金属テルル化物；リン化亜鉛、リン化ガリウム、リン化インジウム、リン化カドミウム等の金属リン化物；ガリウム砒素、銅−インジウム−セレン化物、銅−インジウム−硫化物、シリコン、ゲルマニウム等が挙げられる。さらに、酸化亜鉛／酸化スズ、酸化スズ／酸化チタンのような二種以上の混合物であってもよい。
中でも、酸化チタン、酸化スズ、酸化亜鉛、酸化鉄、酸化タングステン、酸化ジルコニウム、酸化ハフニウム、酸化ストロンチウム、酸化インジウム、酸化セリウム、酸化イットリウム、酸化ランタン、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化ガリウム、酸化ニッケル、チタン酸ストロンチウム、チタン酸バリウム、ニオブ酸カリウム、タンタル酸ナトリウム、酸化亜鉛／酸化スズ、酸化スズ／酸化チタン等の金属酸化物が、比較的安価で入手しやすく、光増感色素が吸着されやすいことから好ましく、とりわけ、酸化チタンが好適である。
Examples of the material of the semiconductor fine particles (2) include titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, cerium oxide, yttrium oxide, lanthanum oxide, and vanadium oxide. , Niobium oxide, tantalum oxide, gallium oxide, nickel oxide, strontium titanate, barium titanate, potassium niobate, sodium tantalate, etc .; silver iodide, silver bromide, copper iodide, copper bromide, etc. Metal halides of: metal sulfides such as zinc sulfide, titanium sulfide, indium sulfide, bismuth sulfide, cadmium sulfide, zirconium sulfide, tantalum sulfide, molybdenum sulfide, silver sulfide, copper sulfide, tin sulfide, tungsten sulfide, and antimony sulfide; selenium Cadmium iodide, zirconium selenide Metal selenides such as zinc selenide, titanium selenide, indium selenide, tungsten selenide, molybdenum selenide, bismuth selenide, lead selenide; cadmium telluride, tungsten telluride, molybdenum telluride, zinc telluride, Metal tellurides such as bismuth telluride; metal phosphides such as zinc phosphide, gallium phosphide, indium phosphide, cadmium phosphide; gallium arsenide, copper-indium-selenide, copper-indium-sulfide, silicon, germanium Etc. Further, it may be a mixture of two or more of zinc oxide / tin oxide and tin oxide / titanium oxide.
Among them, titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, cerium oxide, yttrium oxide, lanthanum oxide, vanadium oxide, niobium oxide, tantalum oxide, gallium oxide, Metal oxides such as nickel oxide, strontium titanate, barium titanate, potassium niobate, sodium tantalate, zinc oxide / tin oxide, tin oxide / titanium oxide are relatively inexpensive and readily available, and photosensitizing dyes Titanium oxide is particularly preferable because it is easily adsorbed.
半導体微粒子の表面に、四塩化チタン水溶液を用いた化学メッキや三塩化チタン水溶液を用いた電気化学的メッキ処理を行ってもよい。このことにより、半導体微粒子の表面積を増大させたり、半導体微粒子近傍の純度を高めたり、半導体微粒子表面に存在する鉄等の不純物を覆い隠したり、又は、半導体微粒子の連結性、結合性を高めたりすることができる。
半導体微粒子は多くの光増感色素を吸着することができるように表面積の大きいものが好ましい。このため、半導体微粒子（２）の層を基板上に塗布した状態での表面積は、投影面積に対して１０倍以上であることが好ましく、さらに１００倍以上であることが好ましい。この上限は、通常、１０００倍程度である。
半導体微粒子（２）の層は、半導体微粒子の単層でもよいが、通常、複数層の半導体微粒子からなり、また、粒径の異なる複数の半導体微粒子からなる層である。
The surface of the semiconductor fine particles may be subjected to chemical plating using a titanium tetrachloride aqueous solution or electrochemical plating using a titanium trichloride aqueous solution. This increases the surface area of the semiconductor fine particles, increases the purity in the vicinity of the semiconductor fine particles, masks impurities such as iron existing on the surface of the semiconductor fine particles, or improves the connectivity and bonding properties of the semiconductor fine particles. can do.
The semiconductor fine particles preferably have a large surface area so that many photosensitizing dyes can be adsorbed. For this reason, the surface area of the semiconductor fine particle (2) applied on the substrate is preferably 10 times or more, more preferably 100 times or more the projected area. This upper limit is usually about 1000 times.
The layer of semiconductor fine particles (2) may be a single layer of semiconductor fine particles, but is usually a layer composed of a plurality of semiconductor fine particles and a plurality of semiconductor fine particles having different particle diameters.
湿式光電気化学電池の場合、通常、導電性基板の上に半導体微粒子層を形成させたのち、該層の微粒子に光増感色素を吸着させる。
導電性基板上に半導体微粒子層を形成する方法としては、半導体微粒子をスプレー噴霧等で直接、導電性基板上に薄膜として形成する方法；導電性基板を電極として電気的に半導体微粒子薄膜を析出させる方法；半導体微粒子のスラリーを導電性基板上に塗布した後、乾燥、硬化又は焼成することによって製造する方法などが例示される。
In the case of a wet photoelectrochemical cell, a semiconductor fine particle layer is usually formed on a conductive substrate, and then a photosensitizing dye is adsorbed on the fine particles of the layer.
As a method for forming a semiconductor fine particle layer on a conductive substrate, a method in which semiconductor fine particles are directly formed as a thin film on a conductive substrate by spraying or the like; a semiconductor fine particle thin film is electrically deposited using a conductive substrate as an electrode Method: A method in which a slurry of semiconductor fine particles is applied on a conductive substrate and then dried, cured, or baked is exemplified.
半導体微粒子のスラリーを導電性基板上に塗布する方法についてさらに詳しく説明すると、例えば、ドクターブレード、スキージ、スピンコート、ディップコートやスクリーン印刷等の手法が挙げられる。これらの手法において、スラリー中の半導体微粒子の分散状態における平均粒径は、０．０１ｎｍ〜１００μｍであることが好ましい。
スラリーを分散させる分散媒としては、半導体微粒子を分散させ得るものであれば特に限定されず、水、又はエタノール、イソプロパノール、ｔ−ブタノールやテルピネオール等のアルコール溶媒；アセトン等のケトン溶媒等の有機溶媒が用いられる。これらの水や有機溶媒は混合物であってもよい。分散液には、ポリエチレングリコール等のポリマー；Ｔｒｉｔｏｎ−Ｘ等の界面活性剤；酢酸、蟻酸、硝酸や塩酸等の有機酸又は無機酸；アセチルアセトン等のキレート剤を含んでいてもよい。
半導体微粒子のスラリーを塗布した導電性基板を焼成することにより、半導体微粒子層を形成することが好ましい。該焼成温度は、通常、導電層又は基板の融点未満で、焼成温度の上限は1200℃であり、好ましくは600℃以下である。また、焼成時間は、通常、１０時間以内である。導電性基板上の半導体微粒子層の厚みは、通常、０．１〜２００μｍであり、好ましくは１〜５０μｍである。
The method for applying the semiconductor fine particle slurry onto the conductive substrate will be described in more detail. Examples thereof include a doctor blade, squeegee, spin coating, dip coating, and screen printing. In these methods, the average particle size in the dispersed state of the semiconductor fine particles in the slurry is preferably 0.01 nm to 100 μm.
The dispersion medium for dispersing the slurry is not particularly limited as long as it can disperse the semiconductor fine particles. Water or an alcohol solvent such as ethanol, isopropanol, t-butanol or terpineol; an organic solvent such as a ketone solvent such as acetone. Is used. These water and organic solvent may be a mixture. The dispersion may contain a polymer such as polyethylene glycol; a surfactant such as Triton-X; an organic acid or inorganic acid such as acetic acid, formic acid, nitric acid or hydrochloric acid; and a chelating agent such as acetylacetone.
It is preferable to form the semiconductor fine particle layer by firing the conductive substrate coated with the semiconductor fine particle slurry. The firing temperature is usually lower than the melting point of the conductive layer or the substrate, and the upper limit of the firing temperature is 1200 ° C., preferably 600 ° C. or less. The firing time is usually within 10 hours. The thickness of the semiconductor fine particle layer on the conductive substrate is usually from 0.1 to 200 μm, preferably from 1 to 50 μm.
導電性基板上に比較的低温で半導体微粒子の層を形成するその他の方法としては、水熱処理を施してポーラスな半導体微粒子の層を形成するHydrothermal法（実用化に向けた色素増感光電気化学電池、第２講（箕浦秀樹）第６３〜６５頁、ＮＴＳ社発行（２００３））、分散された半導体粒子の分散液を基板に電着する泳動電着法（T．Miyasaka et al.,Chem.Lett.,1250(2002)）、半導体ペーストを基板に塗布、乾燥後にプレスするプレス法（実用化に向けた色素増感光電気化学電池、第１２講（萬 雄彦）第３１２〜３１３頁、ＮＴＳ社発行（２００３））等が挙げられる。 Another method for forming a layer of semiconductor fine particles on a conductive substrate at a relatively low temperature is a hydrothermal method in which a layer of porous semiconductor fine particles is formed by hydrothermal treatment (a dye-sensitized photoelectrochemical cell for practical use). 2nd lecture (Hideki Kajiura) 63-65, published by NTS (2003)), electrophoretic electrodeposition method (T. Miyasaka et al., Chem.) Of electrodepositing a dispersion of dispersed semiconductor particles on a substrate. Lett., 1250 (2002)), a method of applying a semiconductor paste to a substrate, pressing after drying (a dye-sensitized photoelectrochemical cell for practical use, 12th lecture (Takehiko Tsuji), pages 312 to 313, NTS Issue (2003)).
本発明に用いられる光増感色素は、可視光領域及び／又は赤外光領域に吸収を持つものであり、種々の金属錯体や有機色素の一種又は二種以上を用いることができる。光増感色素の分子中にカルボキシル基、ヒドロキシアルキル基、ヒドロキシル基、スルホン基、カルボキシアルキル基等の官能基を有する光増感色素が半導体への吸着が早い傾向があることから好ましい。また、光電変換効率や耐久性に優れているため、金属錯体が好ましい。金属錯体としては、銅フタロシアニン、チタニルフタロシアニンなどの金属フタロシアニン、クロロフィル、ヘミン、特開平１−２２０３８０号公報や特表平５−５０４０２３号公報に記載のルテニウム、オスミウム、鉄、亜鉛の錯体を用いることができる。 The photosensitizing dye used in the present invention has absorption in the visible light region and / or the infrared light region, and one or more of various metal complexes and organic dyes can be used. A photosensitizing dye having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, or a carboxyalkyl group in the molecule of the photosensitizing dye is preferred because it tends to be adsorbed to a semiconductor quickly. Moreover, since it is excellent in photoelectric conversion efficiency and durability, a metal complex is preferable. As the metal complex, metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll, hemin, and ruthenium, osmium, iron, and zinc complexes described in JP-A-1-220380 and JP-A-5-504023 are used. Can do.
ルテニウム錯体をさらに詳しく例示すれば、cis-ビス(イソチオシアネート)ビス(2,2'-ビピリジル-4,4'-ジカルボキシレート)-ルテニウム(II) ビス-テトラブチルアンモニウム、cis-ビス(イソチオシアネート)ビス(2,2'-ビピリジル-4,4'-ジカルボキシレート)-ルテニウム(II)、トリス（イソチオシアネート）−ルテニウム(II)-2,2':6',2"-テーピリジン-4,4',4"-トリカルボン酸トリス−テトラブチルアンモニウム、cis-ビス（イソチオシアネート）（2,2'-ビピリジル-4,4'-ジカルボキシレート）(2,2'-ビピリジル-4,4'-ジノニル)ルテニウム(II)などが挙げられる。 More detailed examples of ruthenium complexes include cis-bis (isothiocyanate) bis (2,2'-bipyridyl-4,4'-dicarboxylate) -ruthenium (II) bis-tetrabutylammonium, cis-bis (iso Thiocyanate) bis (2,2'-bipyridyl-4,4'-dicarboxylate) -ruthenium (II), tris (isothiocyanate) -ruthenium (II) -2,2 ': 6', 2 "-thepyridine- Tris-tetrabutylammonium 4,4 ', 4 "-tricarboxylate, cis-bis (isothiocyanate) (2,2'-bipyridyl-4,4'-dicarboxylate) (2,2'-bipyridyl-4, 4'-dinonyl) ruthenium (II) and the like.
有機色素としては、例えば、メタルフリーフタロシアニン、シアニン系色素、メロシアニン系色素、キサンテン系色素、トリフェニルメタン色素、スクアリリウム系色素などが挙げられる。シアニン系色素としては、具体的には、ＮＫ１１９４、ＮＫ３４２２（いずれも日本感光色素研究所製）などが例示される。メロシアニン系色素としては、具体的には、ＮＫ２４２６、ＮＫ２５０１（いずれも日本感光色素研究所製）が挙げられる。キサンテン系色素としては、例えば、ウラニン、エオシン、ローズベンガル、ローダミンＢ、ジブロムフルオレセインなどが挙げられる。トリフェニルメタン色素としては、例えば、マラカイトグリーン、クリスタルバイオレットが挙げられる。
クマリン系色素としては、ＮＫＸ−２６７７（林原生物化学研究所製）（以下の構造式参照）等が挙げられる。
インドリン系等の有機色素として、Ｄ１４９（三菱製紙社製）（以下の構造式参照）等が挙げられる。
Examples of the organic dye include metal-free phthalocyanine, cyanine dye, merocyanine dye, xanthene dye, triphenylmethane dye, squarylium dye, and the like. Specific examples of cyanine dyes include NK1194 and NK3422 (both manufactured by Nippon Photosensitive Dye Research Laboratories). Specific examples of merocyanine dyes include NK2426 and NK2501 (both manufactured by Nippon Photosensitivity Laboratories). Examples of xanthene dyes include uranin, eosin, rose bengal, rhodamine B, dibromofluorescein and the like. Examples of the triphenylmethane dye include malachite green and crystal violet.
Examples of the coumarin dye include NKX-2777 (manufactured by Hayashibara Biochemical Laboratories) (see the following structural formula).
Examples of organic dyes such as indoline include D149 (manufactured by Mitsubishi Paper Industries) (see the following structural formula).
導電性基板に積層された半導体微粒子への光増感色素の吸着方法としては、例えば、本発明の光増感色素を含む溶液中に、よく乾燥した半導体微粒子層及び導電性基板からなる積層体を数時間浸漬する方法が挙げられる。光増感色素の吸着は室温（２５℃）で行ってもよいし、加熱下に行ってもよいし、光増感色素を含む溶液を還流させながら行ってもよい。
光増感色素の吸着方法としては、導電性基板に半導体微粒子層を形成する前に行っても、半導体微粒子と光増感色素を同時に導電性基板に塗布してもよいが、導電性基板に形成された半導体微粒子層に光増感色素を吸着させる方法がより好ましい。半導体微粒子層を加熱処理する場合、光増感色素吸着は加熱処理後に行うことが好ましく、加熱処理後、半導体微粒子層の表面に水が吸着する前に、光増感色素を吸着させる方法が特に好ましい。
As a method for adsorbing a photosensitizing dye to semiconductor fine particles laminated on a conductive substrate, for example, a laminate comprising a well-dried semiconductor fine particle layer and a conductive substrate in a solution containing the photosensitizing dye of the present invention For several hours. Adsorption of the photosensitizing dye may be performed at room temperature (25 ° C.), may be performed under heating, or may be performed while refluxing a solution containing the photosensitizing dye.
The photosensitizing dye can be adsorbed before the semiconductor fine particle layer is formed on the conductive substrate, or the semiconductor fine particles and the photosensitizing dye may be applied to the conductive substrate at the same time. A method of adsorbing the photosensitizing dye to the formed semiconductor fine particle layer is more preferable. When the semiconductor fine particle layer is heat-treated, the photosensitizing dye adsorption is preferably performed after the heat treatment, and a method of adsorbing the photosensitizing dye after the heat treatment and before water is adsorbed on the surface of the semiconductor fine particle layer is particularly preferable. preferable.
半導体微粒子に付着していない光増感色素が浮遊することによる増感効果の低減を抑制するため、未吸着の光増感色素は洗浄によって除去することが望ましい。
吸着する光増感色素は１種類でもよいし、数種混合して用いてもよい。用途が光電気化学電池である場合、太陽光などの照射光の光電変換の波長域をできるだけ広くするように、混合する光増感色素を選ぶことが好ましい。また、光増感色素の半導体微粒子に対する吸着量は、半導体微粒子１ｇに対して０．０１〜１ミリモルが好ましい。このような色素量とすると、半導体微粒子における増感効果が十分に得られ、半導体微粒子に付着していない色素が浮遊することによる増感効果の低減を抑制する傾向にあることから好ましい。
また、半導体微粒子（３）に吸着される光増感色素は、同一でも異なっていてもよい。例えば、第一層目を３００ｎｍ〜５００ｎｍの光増感色素を吸着させ、第二層目に５００ｎｍ〜７００ｎｍの光増感色素を吸着させ、第三層目に７００〜９００ｎｍの光増感色素を吸着させる等の、各層に、吸収波長の異なる光増感色素を吸着させてもよい。
In order to suppress the reduction of the sensitizing effect due to floating of the photosensitizing dye not attached to the semiconductor fine particles, it is desirable to remove the unadsorbed photosensitizing dye by washing.
The photosensitizing dye to be adsorbed may be one kind or a mixture of several kinds. When the application is a photoelectrochemical cell, it is preferable to select a photosensitizing dye to be mixed so that the wavelength range of photoelectric conversion of irradiation light such as sunlight is as wide as possible. Further, the adsorption amount of the photosensitizing dye to the semiconductor fine particles is preferably 0.01 to 1 mmol with respect to 1 g of the semiconductor fine particles. Such a dye amount is preferable because the sensitizing effect in the semiconductor fine particles can be sufficiently obtained and the reduction of the sensitizing effect due to floating of the dye not attached to the semiconductor fine particles tends to be suppressed.
Further, the photosensitizing dyes adsorbed on the semiconductor fine particles (3) may be the same or different. For example, a 300-500 nm photosensitizing dye is adsorbed on the first layer, a 500-700 nm photosensitizing dye is adsorbed on the second layer, and a 700-900 nm photosensitizing dye is adsorbed on the third layer. Photosensitizing dyes having different absorption wavelengths may be adsorbed on each layer, such as adsorbing.
光増感色素同士が会合や凝集等の相互作用することを抑制する目的で、無色の化合物を共吸着させてもよい。共吸着させる疎水性化合物としては、例えば、カルボキシル基を有するステロイド化合物（例えば、ケノデオキシコール酸）等が挙げられる。また、余分な色素の除去を促進する目的で、色素を吸着させた後、アミン類を用いて半導体微粒子の表面を処理してもよい。好ましいアミン類としては、例えば、ピリジン、４−ｔｅｒｔ−ブチルピリジンやポリビニルピリジン等が挙げられる。これらが液体の場合はそのまま用いてもよいし、固体の場合は有機溶媒に溶解して用いてもよい。 A colorless compound may be co-adsorbed for the purpose of suppressing interaction such as association and aggregation between photosensitizing dyes. Examples of the hydrophobic compound to be co-adsorbed include a steroid compound having a carboxyl group (for example, chenodeoxycholic acid). Further, for the purpose of accelerating the removal of excess dye, the surface of the semiconductor fine particles may be treated with amines after adsorbing the dye. Examples of preferable amines include pyridine, 4-tert-butylpyridine, and polyvinylpyridine. When these are liquids, they may be used as they are, or when they are solids, they may be dissolved in an organic solvent.
本発明の電荷移動層に含まれる電解質としては、例えば、Ｉ２と各種ヨウ化物との組合せ、Ｂｒ２と各種の臭化物との組合せ、フェロシアン酸塩−フェリシアン酸塩の金属錯体の組合せ、フェロセン−フェリシニウムイオンの金属錯体の組合せ、アルキルチオール−アルキルジスルフィドのイオウ化合物の組合せ、アルキルビオローゲンとその還元体の組合せ、ポリヒドロキシベンゼン類とその酸化体の組合せ等が挙げられる。
ここで、Ｉ２と組合せ得るヨウ化物としては、例えば、ＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩやＣａＩ２等の金属ヨウ化物；１−プロピル−３−メチルイミダゾリウムアイオダイド、１−プロピル−２，３−ジメチルイミダゾリウムアイドダイド等の４級イミダゾリウム化合物のヨウ素塩；４級ピリジニウム化合物のヨウ素塩；テトラアルキルアンモニウム化合物のヨウ素塩等が挙げられる。
Ｂｒ２と組合せ得るヨウ化物としては、例えば、ＬｉＢｒ、ＮａＢｒ、ＫＢｒ、ＣｓＢｒやＣａＢｒ２等の金属臭化物；テトラアルキルアンモニウムブロマイドやピリジニウムブロマイド等の４級アンモニウム化合物の臭素塩等が挙げられる。
アルキルビオローゲンとしては、例えば、メチルビオローゲンクロリド、ヘキシルビオローゲンブロミド、ベンジルビオローゲンテトラフルオロボレートなどが挙げられ、ポリヒドロキシベンゼン類としては、例えばハイドロキノンやナフトハイドロキノン等が挙げられる。
電解質としては中でも、Ｉ２及びヨウ素化物の組み合わせであることが好ましく、とりわけ、金属ヨウ化物、４級イミダゾリウム化合物のヨウ素塩や４級ピリジニウム化合物のヨウ素塩、及びテトラアルキルアンモニウム化合物のヨウ素塩からなる群から選ばれる少なくとも１種のヨウ化物とＩ２との組合せが好ましい。
Examples of the electrolyte contained in the charge transfer layer of the present invention include a combination of I 2 and various iodides, a combination of Br 2 and various bromides, a combination of ferrocyanate-ferricyanate metal complexes, Examples include combinations of metal complexes of ferrocene-ferricinium ions, combinations of sulfur compounds of alkyl thiol-alkyl disulfides, combinations of alkyl viologens and reduced forms thereof, combinations of polyhydroxybenzenes and oxidized forms thereof.
Here, examples of the iodide that can be combined with I 2 include metal iodides such as LiI, NaI, KI, CsI, and CaI 2 ; 1-propyl-3-methylimidazolium iodide, 1-propyl-2,3 -Iodine salts of quaternary imidazolium compounds such as dimethyl imidazolium idide; iodine salts of quaternary pyridinium compounds; iodine salts of tetraalkylammonium compounds.
Examples of iodide that can be combined with Br 2 include metal bromides such as LiBr, NaBr, KBr, CsBr, and CaBr 2 ; bromine salts of quaternary ammonium compounds such as tetraalkylammonium bromide and pyridinium bromide, and the like.
Examples of alkyl viologen include methyl viologen chloride, hexyl viologen bromide, and benzyl viologen tetrafluoroborate. Examples of polyhydroxybenzenes include hydroquinone and naphthohydroquinone.
Among them, the electrolyte is preferably a combination of I 2 and iodide, and in particular, from metal iodide, iodine salt of quaternary imidazolium compound, iodine salt of quaternary pyridinium compound, and iodine salt of tetraalkylammonium compound. A combination of at least one iodide selected from the group and I 2 is preferred.
本発明の光電気化学電池が湿式である場合、電荷移動層には電解液が含まれる。電解液としては、例えば、水、電解質を溶解する有機溶媒が挙げられる。
有機溶媒としては、例えば、アセトニトリル、メトキシアセトニトリルやプロピオニトリル等のニトリル系溶媒；エチレンカーボネートやプロピレンカーボネート等のカーボネート系溶媒；γ−ブチロラクトン等のラクトン系溶媒；Ｎ，Ｎ−ジメチルホルムアミド等のアミド系溶媒；１−メチル−３−プロピルイミダゾリウムアイオダイドや１−メチル−３−ヘキシルイミダゾリウムアイオダイド；１−エチル−３−メチルイミダゾリウム−ビス（トリフルオロメタンスルホン酸）イミド等のイオン性液体が挙げられる。
電解液は、ポリアクリロニトリル、ポリビニリデンフルオライド、ポリ４−ビニルピリジンやＣｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ,１２４１（１９９８）に示される低分子ゲル化剤でゲル化されていてもよい。
When the photoelectrochemical cell of the present invention is wet, the charge transfer layer contains an electrolyte. Examples of the electrolytic solution include water and an organic solvent that dissolves the electrolyte.
Examples of the organic solvent include nitrile solvents such as acetonitrile, methoxyacetonitrile, and propionitrile; carbonate solvents such as ethylene carbonate and propylene carbonate; lactone solvents such as γ-butyrolactone; amides such as N, N-dimethylformamide Ionic liquids such as 1-methyl-3-propylimidazolium iodide and 1-methyl-3-hexylimidazolium iodide; 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonic acid) imide Is mentioned.
The electrolytic solution may be gelled with a polyacrylonitrile, polyvinylidene fluoride, poly-4-vinylpyridine, or a low-molecular gelling agent shown in Chemistry Letters, 1241 (1998).
本発明の光電気化学電池が乾式である場合、電荷移動層には、固体のホール輸送材料などの固体電解層が用いられる。
固体のホール輸送材料としては、ＣｕＩやＣｕＳＣＮ等の一価の銅を含むｐ型無機半導体からなるものや、Ｓｙｎｔｈｅｔｉｃ Ｍｅｔａｌ，８９,２１５（１９９７）及びＮａｔｕｒｅ,３９５,５８３（１９９８）で示されるような芳香族アミン類；ポリチオフェン及びその誘導体；ポリピロール及びその誘導体；ポリアニリン及びその誘導体；ポリ（ｐ−フェニレン）及びその誘導体；ポリ（ｐ−フェニレンビニレン）及びその誘導体等の導電性高分子からなるものなどが挙げられる。
When the photoelectrochemical cell of the present invention is dry, a solid electrolytic layer such as a solid hole transport material is used for the charge transfer layer.
Examples of solid hole transport materials include those made of p-type inorganic semiconductors containing monovalent copper such as CuI and CuSCN, and those shown in Synthetic Metal, 89 , 215 (1997) and Nature, 395 , 583 (1998). Aromatic amines; Polythiophene and its derivatives; Polypyrrole and its derivatives; Polyaniline and its derivatives; Poly (p-phenylene) and its derivatives; Conductive polymers such as poly (p-phenylene vinylene) and its derivatives Etc.
本発明に用いられる封止剤は、バナジウム、ビスマス又は亜鉛を少なくとも一種を含むガラスフリットを含有するものであり、該ガラスフリットを封止剤として用いることにより、電解液としてアセトニトリル等の揮発性溶媒やヨウ素を用いた場合、それらが特に高温で揮発しにくいため、耐久性が著しく向上する。
バナジウムを含むガラスフリットの組成としては、ZnO、BaO、P2O5、TeO2の少なくとも一種とV2O5とを混合したものが挙げられる。例えば、YEV8-3111、YEV3-4003、YEV8-3018（ヤマト電子株式会社製）が挙げられる。
ビスマスを含むガラスフリットの組成としては、ZnO、P2O5 、B2O3の少なくとも一種とBi2O3とを含む混合系が挙げられる。例えば、ABG-GP-068（TOMATEC社製）が挙げられる。ZnO、P2O5、B2O3以外にも、BaO、CuO、Al2O3、SrO、SiO2、TiO2、Li2O、Na2O,K2O等の成分が混合されていても良い。
亜鉛を含むガラスフリットの組成としては、ZnOとB2O3とを混合したのものが挙げられる。B2O3以外にも、SiO2、Na2O、Li2O、NaF 、P2O5、SnO、K2O、Al2O3、ZrO2、SrO等の成分が混合されていても良い。
これらのガラスフリットには、ケイ酸ジルコニウム、アルミナ、チタニア、シリカ、顔料などがフィラーとして含まれていても良い。
The sealing agent used in the present invention contains a glass frit containing at least one of vanadium, bismuth, or zinc. By using the glass frit as a sealing agent, a volatile solvent such as acetonitrile as an electrolytic solution. When iodine or iodine is used, the durability is remarkably improved because they are not easily volatilized particularly at high temperatures.
Examples of the composition of the glass frit containing vanadium include a mixture of at least one of ZnO, BaO, P 2 O 5 , and TeO 2 and V 2 O 5 . Examples thereof include YEV8-3111, YEV3-4003, and YEV8-3018 (manufactured by Yamato Electronics Co., Ltd.).
Examples of the composition of the glass frit containing bismuth include a mixed system containing at least one of ZnO, P 2 O 5 and B 2 O 3 and Bi 2 O 3 . An example is ABG-GP-068 (manufactured by TOMATEC). In addition to ZnO, P 2 O 5 and B 2 O 3 , components such as BaO, CuO, Al 2 O 3 , SrO, SiO 2 , TiO 2 , Li 2 O, Na 2 O and K 2 O are mixed. May be.
The composition of the glass frit containing zinc includes a mixture of ZnO and B 2 O 3 . In addition to B 2 O 3 , components such as SiO 2 , Na 2 O, Li 2 O, NaF, P 2 O 5 , SnO, K 2 O, Al 2 O 3 , ZrO 2 , SrO may be mixed good.
These glass frits may contain zirconium silicate, alumina, titania, silica, pigments and the like as fillers.
ガラスフリットの線膨張係数としては、貼り合せる基板の線膨張係数に対して±3×10-6/℃の線膨張係数の範囲に入ることが好ましい。基板との線膨張係数の差が大きすぎるとひずみが大きくなるため、張り合わせ時に基板が割れたり、接着不良がおきやすくなるため好ましくない。
これらのガラスフリットは、エチルセルロースやアクリル樹脂等のバインダーをα−テルピネオール等の有機溶剤に溶解したものに混練、分散したペーストとして使用することができる。このペーストは、スクリーン印刷やディスペンサーにより基板等に塗布して使用することができる。
ガラスフリットを用いた封着条件としては、大気下又は窒素やアルゴン等の不活性ガス雰囲気下、焼成温度が約５０℃〜８００℃の範囲で約１０秒〜１２時間加熱することにより行うことができる。焼成は、一定の温度で１回のみで実施しても良いし、バインダーを焼成にて一旦除去した後、封着のため再焼成する等、２回以上に分けて焼成しても良い。
The linear expansion coefficient of the glass frit is preferably in the range of ± 3 × 10 −6 / ° C. relative to the linear expansion coefficient of the substrates to be bonded. If the difference in coefficient of linear expansion from the substrate is too large, the strain becomes large, which is not preferable because the substrate is easily cracked during bonding and poor adhesion is likely to occur.
These glass frit can be used as a paste kneaded and dispersed in a binder such as ethyl cellulose or acrylic resin dissolved in an organic solvent such as α-terpineol. This paste can be used by being applied to a substrate or the like by screen printing or a dispenser.
As sealing conditions using glass frit, it is carried out by heating for about 10 seconds to 12 hours in the atmosphere or in an inert gas atmosphere such as nitrogen or argon at a firing temperature of about 50 ° C. to 800 ° C. it can. Firing may be performed only once at a fixed temperature, or may be performed in two or more steps, such as once the binder is removed by firing and then refired for sealing.
次に、実施例等を挙げて本発明を更に詳細に説明するが、本発明はこれらの例により限定されるものではない。 EXAMPLES Next, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited by these examples.
（実施例１）
導電性基板である、フッ素をドープした酸化スズ膜付き導電性ガラス（日本板硝子製、１０Ω/□、線膨張係数： 8.5×10-6/℃）の導電性面に、酸化チタン分散液であるＴｉ−Ｎａｎｏｘｉｄｅ Ｔ/ＳＰ（商品名、Ｓｏｌａｒｏｎｉｘ社製）をスクリーン印刷を用いて塗布後、５００℃で焼成し、ガラスを冷却して、導電性基板に半導体微粒子層を形成させた。次に、該層の周りに、封止剤としてバナジウムを含むガラスフリットペースト（グレード名： YEV3-4003、ヤマト電子社製、線膨張係数： 7.1×10-6/℃）をディスペンサーにて塗布した。あらかじめドリルにより２箇所に穴をあけた白金蒸着済みのフッ素をドープした酸化スズ膜付き導電性ガラスを重ね合わせ、４９０℃にて焼成した。続いて、cis-ビス（イソチオシアネート）（2,2'-ビピリジル-4,4'-ジカルボキシレート）(2,2'-ビピリジル-4,4'-ジノニル)ルテニウム(II)の溶液（濃度は０．０００３モル／リットル、溶媒はｔ−ブタノール／アセトニトリル＝１／１の混合）に１６時間浸漬し、溶液から取り出したのち、アセトニトリルで洗浄後、自然乾燥させ、導電性基板及び光増感色素を吸着させた半導体微粒子層の積層体を得た。あらかじめ開けておいた対極の穴から電解液（溶媒はアセトニトリル；溶媒中のヨウ素濃度は０．０５モル／リットル、同じくヨウ化リチウム濃度は０．１モル／リットル、同じく４−ｔ−ブチルピリジン濃度は０．５モル／リットル、同じく１−プロピル−２，３−ジメチルイミダゾリウムアイオダイド濃度は０．６モル／リットル）をセル内に注入した。その後、穴を封じるためエチレン−ビニルアルコール共重合樹脂（グレード名： Ｆ１０１，登録商標：エバール、クラレ（株）製）フィルム及びガラス板を穴の上に設置後、電熱プレス機にて熱圧着し封止した光電気化学電池を得た。
このようにして作製した光電気化学電池について、キセノン耐候性試験機に入れ、光照射し（光量： 0.48W/m2（340nm）、ブラックパネル温度：８３℃、湿度：50%RH、雨なし）、変換効率の経時変化を観察した。変換効率の測定は、山下電装社製ソーラーシミュレーターを用いて測定した。
初期の効率を１とした時の７２時間後の変換効率の保持率を表１に示す。
（比較例１）
封止剤として鉛含有ガラスフリット（グレード名：LS-0118、日本電気硝子社製）を用いる以外は、実施例１と同様にして封止セルを得た。次いで、変換効率の経時変化を実施例１と同様にして測定した。結果を表１に示す。
(Example 1)
Titanium oxide dispersion on conductive surface of conductive glass with tin oxide film doped with fluorine (made by Nippon Sheet Glass, 10Ω / □, linear expansion coefficient: 8.5 × 10 -6 / ° C), which is a conductive substrate Ti-Nanoxide T / SP (trade name, manufactured by Solaronix) was applied using screen printing, then baked at 500 ° C., and the glass was cooled to form a semiconductor fine particle layer on the conductive substrate. Next, a glass frit paste (grade name: YEV3-4003, manufactured by Yamato Electronics Co., Ltd., linear expansion coefficient: 7.1 × 10 −6 / ° C.) containing vanadium as a sealant was applied around the layer with a dispenser. . A platinum-deposited fluorine-doped conductive glass with a tin oxide film, which was previously drilled at two locations by a drill, was superposed and fired at 490 ° C. Subsequently, a solution of cis-bis (isothiocyanate) (2,2'-bipyridyl-4,4'-dicarboxylate) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) (concentration Is 0.0003 mol / liter, the solvent is a mixture of t-butanol / acetonitrile = 1/1) for 16 hours, taken out from the solution, washed with acetonitrile, then naturally dried, and the conductive substrate and photosensitization. A laminate of semiconductor fine particle layers adsorbed with the dye was obtained. Electrolytic solution (solvent is acetonitrile; iodine concentration in the solvent is 0.05 mol / liter, lithium iodide concentration is 0.1 mol / liter, and 4-t-butylpyridine concentration is from the counter electrode hole that has been opened in advance. Was 0.5 mol / liter, and the concentration of 1-propyl-2,3-dimethylimidazolium iodide was 0.6 mol / liter). After that, an ethylene-vinyl alcohol copolymer resin (grade name: F101, registered trademark: Eval, manufactured by Kuraray Co., Ltd.) film and a glass plate are placed on the hole and then thermocompression bonded with an electric heat press to seal the hole. A sealed photoelectrochemical cell was obtained.
The thus produced photoelectrochemical cell was put into a xenon weathering tester and irradiated with light (light intensity: 0.48 W / m 2 (340 nm), black panel temperature: 83 ° C., humidity: 50% RH, no rain ), The change in conversion efficiency over time was observed. The conversion efficiency was measured using a solar simulator manufactured by Yamashita Denso.
Table 1 shows the conversion efficiency retention ratio after 72 hours when the initial efficiency is 1.
(Comparative Example 1)
A sealing cell was obtained in the same manner as in Example 1 except that lead-containing glass frit (grade name: LS-0118, manufactured by Nippon Electric Glass Co., Ltd.) was used as the sealing agent. Subsequently, the change with time of the conversion efficiency was measured in the same manner as in Example 1. The results are shown in Table 1.
（実施例２）
導電性基板である、フッ素をドープした酸化スズ膜付き導電性ガラス（日本板硝子製、１０Ω/□、線膨張係数： 8.5×10-6/℃）の周囲に、封止剤としてバナジウムを含むガラスフリットペースト（グレード名： YEV3-4003、ヤマト電子社製）をディスペンサーにて塗布後、あらかじめドリルにより穴をあけた導電性基板である、フッ素をドープした酸化スズ膜付き導電性ガラス（旭硝子製、１０Ω/□）を重ね合わせた。４９０℃で焼成後、あらかじめ開けておいた対極の穴から電解液（溶媒はアセトニトリル；溶媒中の沃素濃度は０．０５モル／リットル、同じくヨウ化リチウム濃度は０．１モル／リットル、同じく４−ｔ−ブチルピリジン濃度は０．５モル／リットル、同じく１−プロピル−２，３−ジメチルイミダゾリウムアイオダイド濃度は０．６モル／リットル）をセル内に注入した。その後、穴を封じるためエチレン−ビニルアルコール共重合樹脂（グレード名： Ｆ１０１，登録商標：エバール、クラレ（株）製）フィルム及びガラス板を穴の上に設置後、電熱プレス機にて熱圧着し封止した。
電解液を封入したガラス板を８５℃のオーブンでエージングし、その際のヨウ素の経時変化を３６２nmの吸光度で測定した。初期の吸光度を１とした時の３３０時間後の吸光度の保持率を表２に示す。吸光度が大きいほど、光電気化学電池に封入されたヨウ素の保持率が高いことを意味する。
(Example 2)
Glass containing vanadium as a sealant around a conductive substrate, conductive glass with tin oxide film doped with fluorine (made by Nippon Sheet Glass, 10Ω / □, linear expansion coefficient: 8.5 × 10 -6 / ° C) After applying frit paste (grade name: YEV3-4003, manufactured by Yamato Electronics Co., Ltd.) with a dispenser, conductive glass with tin oxide film doped with fluorine (made by Asahi Glass, which is a conductive substrate previously drilled with a drill) 10Ω / □) were superimposed. After firing at 490 ° C., the electrolyte solution (solvent is acetonitrile; iodine concentration in the solvent is 0.05 mol / liter, lithium iodide concentration is 0.1 mol / liter, also 4 -T-butylpyridine concentration was 0.5 mol / liter, and 1-propyl-2,3-dimethylimidazolium iodide concentration was 0.6 mol / liter). After that, an ethylene-vinyl alcohol copolymer resin (grade name: F101, registered trademark: Eval, manufactured by Kuraray Co., Ltd.) film and a glass plate are placed on the hole and then thermocompression bonded with an electric heat press to seal the hole. Sealed.
The glass plate encapsulating the electrolyte was aged in an oven at 85 ° C., and the time course of iodine at that time was measured by absorbance at 362 nm. Table 2 shows the absorbance retention after 330 hours when the initial absorbance is 1. It means that the higher the absorbance, the higher the retention rate of iodine encapsulated in the photoelectrochemical cell.
（実施例３）
封止剤として ビスマス含有ガラスフリット（グレード名：ABG-GP-068、TOMATEC社製、線膨張係数： 7.0×10-6/℃）を用いる以外は、実施例２と同様に実施した。結果を表２に示す。
(Example 3)
This was carried out in the same manner as in Example 2 except that bismuth-containing glass frit (grade name: ABG-GP-068, manufactured by TOMATEC, linear expansion coefficient: 7.0 × 10 −6 / ° C.) was used as the sealant. The results are shown in Table 2.
（実施例４）
封止剤として亜鉛含有ガラスフリット（グレード名：G3-4480、奥野製薬製、線膨張係数： 9.0×10-6/℃）を用いる以外は、実施例２と同様に実施した。
Example 4
The same procedure as in Example 2 was performed except that a zinc-containing glass frit (grade name: G3-4480, manufactured by Okuno Pharmaceutical Co., Ltd., linear expansion coefficient: 9.0 × 10 −6 / ° C.) was used as the sealant.
（比較例２）
封止剤として鉛含有ガラスフリット（グレード名：LS-0118、日本電気硝子社製）を用いる以外は、実施例２と同様にして電解液を封入したガラス板を得た。次いで、吸光度の経時変化を実施例２と同様にして測定した。結果を表２に示す。
(Comparative Example 2)
A glass plate enclosing an electrolyte solution was obtained in the same manner as in Example 2 except that lead-containing glass frit (grade name: LS-0118, manufactured by Nippon Electric Glass Co., Ltd.) was used as the sealant. Next, the change in absorbance with time was measured in the same manner as in Example 2. The results are shown in Table 2.
本発明の光電気化学電池は、従来の封止剤を用いた場合と比較して、高温下での使用や長期間の使用でもヨウ素などの電解質や揮発性溶媒の消失が著しく低減されることから、耐久性に優れる。このような優れた特性から、太陽光による太陽電池、トンネルや屋内での人工光による光電気化学電池に用いることができる。また、本発明の光電気化学電池は、光の照射を受けて電流が流れることから、光センサーとして用いることができる。 In the photoelectrochemical cell of the present invention, the disappearance of electrolytes such as iodine and volatile solvents is remarkably reduced even when used at a high temperature or for a long period of time compared to the case where a conventional sealant is used. Therefore, it has excellent durability. Because of such excellent characteristics, it can be used in solar cells using sunlight, photoelectrochemical cells using artificial light in tunnels and indoors. In addition, the photoelectrochemical cell of the present invention can be used as an optical sensor because current flows upon receiving light irradiation.
１ 基板
２ 導電層
３ 半導体粒子層
４ 光増感色素
５ 電解液
６ 導電層
７ 基板
８ 導電性基板
９ 対極
１０ 封止剤
DESCRIPTION OF SYMBOLS 1
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| JP2009274948A (en) * | 2008-04-18 | 2009-11-26 | Nippon Electric Glass Co Ltd | Glass composition for dye-sensitized solar cell and material for dye-sensitized solar cell |
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| JP2011086518A (en) * | 2009-10-16 | 2011-04-28 | Nippon Electric Glass Co Ltd | Glass composition for dye-sensitized solar cell, and material for dye-sensitized solar cell |
| US8551368B2 (en) | 2009-10-28 | 2013-10-08 | Shoei Chemical Inc. | Conductive paste for forming a solar cell electrode |
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| JP2006524419A (en) * | 2003-04-16 | 2006-10-26 | コーニング インコーポレイテッド | Glass package sealed with frit and manufacturing method thereof |
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| JP2003192378A (en) * | 2001-12-25 | 2003-07-09 | Yamato Denshi Kk | Lead-free low-melting glass for sealing |
| JP2006524419A (en) * | 2003-04-16 | 2006-10-26 | コーニング インコーポレイテッド | Glass package sealed with frit and manufacturing method thereof |
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| JP2009274948A (en) * | 2008-04-18 | 2009-11-26 | Nippon Electric Glass Co Ltd | Glass composition for dye-sensitized solar cell and material for dye-sensitized solar cell |
| WO2010125929A1 (en) * | 2009-04-30 | 2010-11-04 | シャープ株式会社 | Porous electrode, dye-sensitized solar cell, and dye-sensitized solar cell module |
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| JP2011086518A (en) * | 2009-10-16 | 2011-04-28 | Nippon Electric Glass Co Ltd | Glass composition for dye-sensitized solar cell, and material for dye-sensitized solar cell |
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